湖南砂矿金刚石中顺磁氮的分配特点和金刚石归类问题

利用EPR检测了200多颗湖南砂矿金刚石。为53颗晶体测定了顺磁N的含量。阐明了砂矿金刚石中顺磁N分配的一般特点:具顺磁N信号者占30％,具较大顺磁N含量(10~(17)—10~(18)N原子/cm~3)者只占7％,属I_b型的晶体～2％。通过顺磋和红外光谱资料对比,发现了一些奇异现象,设想后者起因于混型晶的存在。为使金刚石正确归类,给出了一套测试方案,强调了紫外、红外光谱,紫外形貌照相和EPR等手段的联合使用。     

The microscopic structure of the oxygen–aluminium hole center in natural and neutron irradiated blue topaz

The dominant O⁻ hole center in natural and neutron irradiated blue topaz with general formula Al₂SiO₄(F,OH)₂ has been investigated with electron paramagnetic resonance (EPR) and optical absorption. The analysis of the EPR spectra of the O⁻ center yielded superhyperfine interactions with two equivalent Al neighbors in four magnetically inequivalent positions. From the g-factors it is found that the O⁻ hole center is located in (8d) Wyckoff positions on fluoride sites that were substituted by hydroxyl molecules prior to the irradiation. The spin Hamiltonian parameters were successfully interpreted with the model of transferred hyperfine interaction by exchange polarization supporting the localization of O⁻ in (F,OH)⁻ sites. The O⁻ center has the same thermal stability as the absorption band centered at 620 nm, which is responsible for the blue color. The intensity of the absorption band correlates linearly with the O⁻ concentration. Its correlation with the blue color is discussed.     

硅酸钡铜的光吸收谱和EPR谱

本文报道水热合成硅酸钡铜(BaCuSi_4O_(10))的光吸收谱和EPR谱。EPR测量表明,在硅酸钡铜中,Cu~(2 )离子位置有轴对称性。在这种对称性下,一般只能观察到三条Cu~(2 )离子的吸收谱带,但在BaCuSi_4O_(10)的吸收谱中却观察到了四条。这一矛盾用~2Eg激发态的动态Jahn-Teller效应来解释。本文提出的~2Eg和~2A_1g能级的相对次序与文献[2]的相反,文中对这一问题作了详细的分析。跃迁频率和g因子的计算值在实验误差范围内与观测值一致。     

Electron paramagnetic resonance studies on clinochlore from Longitudinal Valley area,northeastern Taiwan

A natural sample of clinochlore from the Longitudinal Valley area of northeastern Taiwan has been characterized by using the powder X-ray diffraction (XRD), differential thermal analysis and electron paramagnetic resonance (EPR) spectroscopic techniques. The lattice parameters of the monoclinic (IIb) clinochlore with the composition (Mg_2.988 Al_1.196 Fe_1.6845 Mn_0.026)_5.8945 (Si_2.559 Al_1.441)₄ O₁₀ (OH)₈ have been calculated from the powder XRD data and are found to be a = 5.347 Å, b = 9.223 Å, c = 14.250 Å, β = 97.2° and Z = 2. The thermal behaviour of the sample showed the typical behaviour of clinochlore with a hydroxyl content of 12.5 wt%. The EPR spectrum at room temperature exhibits two resonance signals centred at g ≈ 2.0 and g ≈ 8.0. The signal at g ≈ 2.0 shows a six-line hyperfine structure which is a characteristic of Mn²⁺ ions in octahedral symmetry. The resonance signal at g ≈ 8.0 is a characteristic of Fe³⁺ ions. The EPR spectra have also been recorded at different temperatures (123–295 K). The population of spin levels (N) has been calculated for g ≈ 2.0 and g ≈ 8.0 resonance signals. It is observed that N increases with decreasing temperature. From EPR spectra, the spin-Hamiltonian parameters have been evaluated. The zero-field splitting parameter (D) is found to be temperature dependent. The peak-to-peak width of the g ≈ 8.0 resonance signal is found to increase with decrease in temperature.     

EPR evidence for maghemitization of magnetite in a tropical soil

Electron paramagnetic spectroscopy (EPR) was used in combination with standard rock magnetic methods to study magnetic minerals in a tropical soil. The susceptibility and hysteresis measurements showed magnetite grains with a Curie temperature near 850 K as the dominant magnetic remanence carriers in the soil. A minor Ti content in the magnetite was found by energy dispersive X-ray analysis. In order to get insight into the weathering status of the magnetite, different chemical treatments, including oxalate and citrate–bicarbonate–dithionite (CBD) extraction, were applied to the soil samples. The hysteretic properties exhibited no significant differences between the untreated and the CBD or oxalate treated samples. By contrast, the comparison of the EPR spectra revealed a significant broadening of the linewidth (δB) and a shift of the g -values ( g _eff) to lower fields after the CBD treatment. Furthermore, the spectral parameters g _eff and δB exhibited an angular dependence. At low temperature, the CBD treated samples showed a jump in δB between 120 and 100 K, the temperature range characteristic for the Verwey transition in magnetite. The changes in the spectral properties after the CBD treatment, which dissolves ferric oxides, were attributed to the removal of maghemite formed by the oxidation of magnetite, that is, during the maghemitization of the magnetite grains.     

Ionizing radiation-induced defects in smectite clays

 The interaction of γ-rays with smectites induces paramagnetic defects in the structure of these clay minerals. The EPR spectra of three different smectites detect the creation of structural defects and trapping of organic free radicals in the clay structure upon irradiation. The defects are assigned to positive holes or trapped electrons stabilised by existing local charge imbalances in the mineral lattice. The organic radicals are derived from organic compounds present as impurities in the crystal lattice of the clay minerals. In addition, γ-rays cause migration of small interlayer cations (such as Li⁺) into the layers, as clearly evidenced by EPR and FT-IR reflectance spectroscopies. Received: 20 April 2000 / Accepted: 2 December 2000     

海岸带水体氮、磷的测定方法与准确测定

利用湛江东北海岸近30a6期LandSatTM/OLI遥感影像,基于人机交互方式获取海岸线空间信息,综合运用端点变率(EndPointRate,EPR)、线性回归变率(LinearRegressionRate,LRR)、岸线类型结构等多种方法或指标对湛江东北海岸线时空变迁及主要驱动因素进行了深入分析。结果表明:近30a湛江东北大陆海岸线长度共增长约27.56km,岛屿海岸线长度共增长约15.44km,海岸线类型较多,自然海岸线锐减,利用类型构成趋于复杂,且更多地受到了人类活动干扰;海岸线变迁方向整体以向海扩张为主,其中大陆海岸线的平均 LRR和 EPR 为4.18m/a和4.12m/a,最高 LRR达94.26m/a;岛屿海岸线的平均 LRR和 EPR为2.24m/a和3.79m/a,最高 LRR 达66.44m/a。海岸线摆动剧烈区域主要集中于受围填海工程等人类工程活动影响较为显著的岸段。人类活动已成为湛江东北海岸线变迁的主导因素。     

Radiation-damage-induced defects in quartz. I. Single-crystal W-band EPR study of hole centers in an electron-irradiated quartz

Single-crystal W-band electron paramagnetic resonance (EPR) spectra of an electron-irradiated quartz, measured at room temperature, 110 and 77 K, disclose three previously reported hole centers (#1, G and an ozonide radical). The W-band EPR spectra of these three centers clearly resolve six magnetically nonequivalent sites each, whereas previous X- and Q-band EPR studies reported Centers #1 and the ozonide radical to consist of only three symmetry-related components and interpreted them to reside on twofold symmetry axes in the quartz structure. The calculated g matrices of Center #1 and the ozonide radical show that deviations from twofold symmetry axes are <10°, which are probably attributable to distortion related to neighboring charge compensating ions. The W-band EPR spectra of Center G not only result in improved g matrices but also allow quantitative determination of the nuclear hyperfine (A) and quadrupole (P) matrices of its ²⁷Al hyperfine structure that was incompletely resolved before. In particular, the g-maximum and g-minimum principal axes of Center G are approximately along two pairs of O–O edges of the SiO₄ tetrahedron, while the unique A principal axis is approximately along a Si–Si direction. These new spin-Hamiltonian parameters suggest that Center G most likely involves trapping of a hole between two oxygen atoms related to a silicon vacancy and stabilized by an Al³⁺ ion in the neighboring tetrahedron (hence an O₂ⁿ⁻–Al³⁺ defect, where n is either 1 or 3).     

东太平洋海隆(EPR)13°N热液区附近沉积物粒度特征

2003年中国海底热液硫化物调查航段在EPR西侧取得了E271与E272站位的小箱体柱状样品,通过对这些样品采用酸化和未酸化两种前处理方法的粒度分析,结果表明样品受热液活动影响不强烈;粒度分布曲线表现为多峰分布,为多种物源共同叠加沉积的结果,其中以生物源与火山源为主。因此该地区的沉积物源虽然有热液活动的贡献,但是较其它来源的沉积物所占的比例较小。     

Identification and valuation of paramagnetic radicals in natural dolomites as an indicator of geological events

 Geological sedimentary dolomite samples from the Superior Proterozoic are studied using electron paramagnetic resonance (EPR) spectroscopy. The complex spectra in the g=2.0 region is composed of Mn²⁺ lines and signals due to crystallization and radiation-induced defects. Measurements in microwave frequencies of 9.5 GHz (X-band) and 35 GHz (Q-band), and thermal and/or radiation treatments allowed identification of seven paramagnetic radicals in the g=2.0 region: (1) isotropic organic radical; (2) axial SO₂ ⁻; (3) axial PO₂ ⁰ or PO₂ ²⁻; (4) isotropic CO₂ ⁻; (5) axial CO₂ ⁻; (6) axial CO₃ ³⁻; (7) isotropic unknown line. The use of these paramagnetic centres as indicators of geological events is discussed. Received: 18 March 2002 / Accepted: 3 October 2002